EP0542105B1 - Combinaison aqueuse de liants, procédé de sa préparation et son utilisation - Google Patents

Combinaison aqueuse de liants, procédé de sa préparation et son utilisation Download PDF

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Publication number
EP0542105B1
EP0542105B1 EP92118831A EP92118831A EP0542105B1 EP 0542105 B1 EP0542105 B1 EP 0542105B1 EP 92118831 A EP92118831 A EP 92118831A EP 92118831 A EP92118831 A EP 92118831A EP 0542105 B1 EP0542105 B1 EP 0542105B1
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Prior art keywords
groups
acid
component
hydroxyl
bis
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English (en)
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EP0542105B2 (fr
EP0542105A1 (fr
Inventor
Harald Dr. Blum
Werner Dipl.-Ing. Kubitza
Joachim Dr. Probst
Michael Dr. Sonntag
Volker Dr. Schneider
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

Definitions

  • the invention relates to an aqueous binder combination based on mixtures of water-dispersible or soluble polyol components, consisting of at least two different hydroxyl-containing polymers based on polyester and / or polymer, and polyisocyanates, a process for the preparation of such binder combinations and their use as binders in paints, Coating and sealing compounds.
  • the concentration of water-originating, active hydrogen atoms in such systems is of course much higher than the concentration of hydroxyl groups of the organic, NCO-reactive component, so that it must be assumed that polyisocyanate / organic polyhydroxyl compound / water are present in the ternary system All in all, an isocyanate-water reaction takes place with the formation of urea and carbon dioxide, which on the one hand does not lead to the crosslinking of the organic polyhydroxyl compounds and on the other hand to the foaming of the paint preparation due to the formation of carbon dioxide.
  • aqueous polymer polyols consisting of at least two different hydroxyl-containing polymers based on polyester and / or polymer and polyisocyanates with free isocyanate groups can also be used as paint binders, which assist in the production of paints with a long processing time and excellent flow allow film formation and good pigment wettability.
  • the invention also relates to a process for the preparation of such an aqueous binder combination, which is characterized in that in an aqueous solution or dispersion of a polyol component which comprises a mixture of at least two individual components selected from A1), A2), A3), A4) and A5) of the type mentioned above, emulsifies a polyisocyanate component having a viscosity at 23 ° C.
  • the invention also relates to the use of the binder combinations essential to the invention as binders for lacquers, coating and sealing compounds, and for adhesives.
  • Component A) is an aqueous solution or dispersion (in general, both dissolved and dispersed particles are present at the same time) of a polyol component, which in turn is a mixture.
  • the aqueous solution or dispersion generally has a water content of 35 to 80, preferably 45 to 70% by weight.
  • the polyol mixtures which are dissolved and / or dispersed in component A) essentially consist of at least two hydroxyl-containing polymers, selected from different groups A1), A2), A3), A4) and A5), at least two of these mixtures
  • Polymers containing hydroxyl groups from different groups must be present in each case at least 5% by weight, preferably at least 15% by weight, based on the total weight of the mixture.
  • hydroxyl-containing polymers from one of the groups A1) to A5) to be used, provided that the mixture contains at least two of the groups mentioned in the specified minimum amount.
  • additional hydroxy-functional polymers for example based on polyether, polyurethane and / or polyepoxide or also reactive diluents, ie in particular water-soluble polyhydric alcohols with a molecular weight in the range from 62 to 200, such as ethylene glycol, glycerol and / or trimethylolpropane.
  • Component A1 comprises urethane, carboxylate and hydroxyl group-containing polyester resins, which preferably have a molecular weight Mw (weight average) of 3000 to 100,000, in particular 6000 to 50,000, a hydroxyl number of which can be determined according to gel permeation chromatography using calibrated polystyrene as standard 20 to 240, preferably from 45 to 190 mg KOH / g substance, an acid number (based on all carboxyl groups, 25 to 100, preferably 40 to 100% of the salt form, ie the carboxylate form) of 8 to 60 , preferably from 11 to 40 mg KOH / g substance and a urethane group content from 1.0 to 15.0, preferably from 4.0 to 12.5% by weight, the values for hydroxyl number, acid number and urethane group content each refer to solid resin.
  • Mw molecular weight average
  • Component A1 is generally used in the form of 20 to 65, preferably 30 to 55% by weight aqueous solutions or dispersions in the preparation of the binder combination according to the invention, which generally have a viscosity of 10 to 30,000, preferably 50 to 10,000 mPa.s at 23 ° C and pH values of 3 to 10, preferably 6 to 9.
  • the polyester resins A1) Depending on the molecular weight of the polyester resins A1) containing urethane, carboxylate and hydroxyl groups, the content of carboxyl or carboxylate groups, and the type of neutralizing agent used and any auxiliary solvents used, the polyester resins A1) are available as a solution or as a dispersion, in general, however, both dissolved and dispersed fractions are present.
  • Dissolving step by adding a base to 25 to 100% are converted into carboxylate groups and the organic solvent is optionally partially or completely removed from the reaction mixture before, during or after the preparation of the dispersion or solution.
  • Suitable monocarboxylic acids a1) are, for example, benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid, saturated fatty acids such as e.g. 2-ethylhexanoic acid, isononanoic acid, coconut oil fatty acid, hydrogenated technical fatty acids or fatty acid mixtures, decanoic acid, dodecanoic acid, tetradecanoic acid, stearic acid, palmitic acid, docosanoic acid, unsaturated fatty acids, e.g. Soybean oil fatty acid, sorbic acid, peanut oil fatty acid, conjuene fatty acids, tall oil fatty acid, safflower oil fatty acid and mixtures of these or other monocarboxylic acids.
  • saturated fatty acids such as e.g. 2-ethylhexanoic acid, isononanoic acid, coconut oil fatty acid, hydrogenated technical fatty acids or fatty acid mixture
  • Suitable higher-functionality carboxylic acids a2) or anhydrides are, for example, phthalic acid (anhydride), isophthalic acid, terephthalic acid, tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), maleic acid (anhydride), succinic acid (anhydride),), fumaric acid, adipic acid, azainic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, sebacic acid, , Trimer fatty acids, trimellitic acid (anhydride), pyromellitic acid (anhydride) and mixtures of these or other acids.
  • Suitable polyhydric alcohols a3) are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-, 1,4-, 2,3-butanediol, 1,6-hexanediol, 2,5-hexanediol, trimethylhexanediol, diethylene glycol, triethylene glycol, hydrogenated bisphenols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, tricyclodecanediol, 1,4-butanediol, trimethylpropane , Glycerin, pentaerythritol, trimethylpentanediol, dipentaerythritol and mixtures of these or other polyhydric alcohols.
  • Suitable monohydric alcohols a4) are, for example, n-hexanol, cyclohexanol, decanol, dodecanol, tetradecanol, octanol, octadecanol, natural fatty alcohol mixtures such as e.g. Ocenol 110/130 (from Henkel) and mixtures of these and other alcohols.
  • Suitable starting components a5) are, for example, dimethylolpropionic acid, lactic acid, malic acid, tartaric acid, ⁇ -hydroxycaproic acid, castor oil fatty acid or ⁇ -caprolactone.
  • Suitable starting components a6) are, for example, aminoethanol, 2-aminopropanol, diethanolamine, aminoacetic acid or 6-aminohexanoic acid.
  • the starting component b) is at least one compound of the molecular weight range 32 to 2000 which is different from the compounds a) and c) and which is mono- to tetrafunctional in the sense of the isocyanate addition reaction and has amino and / or hydroxyl groups.
  • Suitable compounds are Mono alcohols such as methanol, n-butanol, n-butyl glycol, n-hexanol, stearyl alcohol, the isomeric octadecenols or octadecadienols, benzyl alcohol; dihydric alcohols such as neopentyl glycol, 1,6-hexanediol, 1,4-bis-hydroxymethyl-cyclohexane; trihydric alcohols such as glycerol or trimethylolpropane; tetravalent alcohols such as pentaerythritol, and the alkoxylation products of such alcohols; furthermore amino alcohols such as ethanol, diethanolamine, aminomethylpropanol or amines such as N-methylcyclohexylamine, Stearylamine, diethylenetriamine, 1,6-diaminohexane or isophoronediamine.
  • Mono alcohols such as methanol,
  • Component c) is at least one 2,2-bis (hydroxymethyl) alkanecarboxylic acid with a total of at least 5 carbon atoms, preferably 2,2-bis (hydroxymethyl) propionic acid (dimethylolpropionic acid) or a t-amine salt such acid, for example around the triethylamine salt of dimethylolpropionic acid.
  • Component d) or g) is at least one, at least difunctional, isocyanate component with a molecular weight in the range from 168 to 1500.
  • isocyanate component with a molecular weight in the range from 168 to 1500.
  • hexamethylene diisocyanate, perhydro-2,4- and -4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate are suitable and other isocyanates such as in "Methods of Organic Chemistry” (Houben-Weyl, Vol. 14/2, 4th edition, Georg Thieme Verlag Stuttgart 1963, pp. 61 to 70).
  • lacquer polyisocyanates based on hexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate which have, for example, urethane groups, uretdione groups, isocyanurate and or or biuret groups.
  • Hexamethylene diisocyanate, isophorone diisocyanate and lacquer polyisocyanates based on hexamethylene diisocyanate, such as those described in the description of component B) are preferably used. Mixtures of the polyisocyanates mentioned and also the other polyisocyanates are also suitable.
  • the starting components f) and i) are at least one anhydride of a di-, tri- and, or tetracarboxylic acid, e.g. Tetrahydrophthalic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride and / or pyromellitic acid anhydride.
  • a di-, tri- and, or tetracarboxylic acid e.g. Tetrahydrophthalic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride and / or pyromellitic acid anhydride.
  • Suitable starting components a7) are, for example, lithium, potassium, sodium, magnesium, calcium or t-amine salts of 5-sulfoisophthalic acid, sulfobenzoic acid, sulfophthalic acid, dimethylsulfoisophthalic acid, 3-hydroxy-5-sulfobenzoic acid and 2- Hydroxy-5-sulfobenzoic acid, sulfonate diols of the type disclosed, for example, in DE-OS 2 446 440 are also suitable as starting component a7).
  • Preferably used as starting component a7) are the sulfonates obtainable by neutralization of the sulfonic acid group of aromatic sulfocarboxylic acids of the molecular weight range 224 to 360 with lithium, potassium or sodium hydroxide or carbonate or bicarbonate or with carboxyl groups with t-amines.
  • suitable tertiary amines for neutralizing the sulfonic acid groups are triethylamine, N, N-dimethylethanolamine, N-methyldiethanolamine or other tertiary amines.
  • Basically possible, but less preferred is the use of corresponding free carboxyl and sulfonic acid groups when carrying out the polycondensation reaction with subsequent, at least partial neutralization of the sulfonic acid groups incorporated in this way into the polyester resins.
  • Suitable organic solvents for the preparation of the polyester resins A1) to A3) are, for example, N-methylpyrrolidone, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetone, xylene, toluene, butyl acetate or mixtures of these or other solvents.
  • the organic solvents used can be wholly or partly, if appropriate, before, during or after the dispersing step can be removed azeotropically and / or by applying a vacuum or an increased inert gas stream from the reaction mixture.
  • Suitable catalysts for a urethanization reaction can e.g. be: tertiary amines such as Triethylamine, stannous octoate, dibutyltin oxide, dibutyltin dilaurate and other common catalysts.
  • Suitable catalysts for an esterification reaction can e.g. be: dibutyltin oxide, sulfuric acid, para-toluenesulfonic acid,
  • the incorporated acid groups are at least partially, preferably 25 to 100, particularly preferably 40 to 100% converted into the salt form.
  • Bases suitable for this neutralization are, for example, ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, sodium hydroxide, lithium hydroxide and potassium hydroxide.
  • the neutralizing agents can also be used in a stoichiometric excess.
  • organic solvents or reactive diluents such as ethanol, propanol, ethylene glycol, propylene glycol, butanol, butyl glycol, hexanol, octanol, butyl diglycol, glycerol can also be obtained to achieve certain properties.
  • Ethyl diglycol, methyl diglycol and methoxypropanol can be added.
  • the water / neutralizing agent mixture can alternatively be added to the resin, water to the resin / neutralizing agent mixture, the resin to the water / neutralizing agent mixture or the resin / neutralizing agent mixture to the water.
  • the dispersibility of the resins in water can, if desired, be achieved by using external emulsifiers such as e.g. ethoxylated nonylphenol can be improved when dispersing.
  • the dispersing step is usually carried out at 40 to 120 ° C.
  • the aqueous solutions or dispersions of the polyester resins A1) to A3) which can be used to prepare the polyol component A) according to the invention generally have a solids content of 20 to 65, preferably 30 to 55% by weight.
  • Their content of (inert to isocyanate groups) solvents and (reactive to isocyanate groups) reactive thinners is generally a total of at most 8, preferably at most 6 and particularly preferably at most 1.5% by weight.
  • the polyol component A4) is hydroxyl groups, sulfonate and / or carboxylate groups, preferably carboxylate groups and optionally sulfonic acid and / or carboxyl groups, preferably carboxyl group-containing polymers of olefinically unsaturated monomers, which are preferably according to the Gel permeation chromatography using polystyrene as the standard determinable molecular weight Mw (weight average) from 500 to 100,000, in particular 1000 to 50,000, a hydroxyl number from 16.5 to 264, preferably 33 to 165 mg KOH / g solid resin and an acid number (based on all Carboxyl and sulfonic acid groups, which are 25 to 100% in the salt form), from 5 to 125 mg KOH / g solid.
  • These anionic groups are particularly preferably carboxylate groups.
  • the polymer resins A4) are generally used in the preparation of the coating compositions according to the invention in the form of 10- to 50-, preferably 20 to 40% by weight, aqueous solutions and / or dispersions which generally have a viscosity of 10 to 105 , preferably 100 to 10,000 mPa.s / 23 ° C and pH values of 5 to 10, preferably 6 to 9.
  • the aqueous systems containing the polymers are real dispersions, colloidally dispersed or molecularly dispersed dispersions, but generally so-called "partial dispersions", that is, aqueous systems that are partly molecularly dispersed and partly colloidally dispersed.
  • the hydroxyl-containing polymers are also prepared by copolymerization of olefinically unsaturated monomers known per se, the monomers being both hydroxyl-containing monomers n) and acid groups, i.e. Sulfonic acid groups or carboxyl groups, preferably monomers m) having carboxyl groups, are generally copolymerized together with further monomers o), after which the acid groups present are at least partially neutralized.
  • the monomers containing acid groups are also used for the purpose of incorporating carboxyl and / or sulfonic acid groups into the copolymers which, owing to their hydrophilicity, ensure the water solubility or dispersibility of the polymers, in particular after at least partial neutralization of the acid groups.
  • the amount of the "acid” comonomers used and the degree of neutralization of the "acid" polymers initially obtained correspond to the information given above with regard to the acid number and the content of sulfonate and / or carboxylate groups.
  • the "acidic" comonomers are used in amounts of 0.3 to 30, preferably 1 to 20,% by weight, based on the total weight of the monomers used.
  • aqueous dispersions generally result even after complete neutralization, in which at most a small amount of polymer is present in a molecularly dispersed solution. If one goes to higher contents of "acidic” monomers with a constant degree of neutralization, the result is increasing proportions of molecularly dispersed dissolved species, until finally the colloid-disperse fractions disappear at contents of more than approx. 12% by weight.
  • Suitable “acidic” comonomers m) are in principle all olefinically unsaturated, polymerizable compounds which have at least one carboxyl and / or sulfonic acid group, such as, for example, olefinically unsaturated mono- or dicarboxylic acids in the molecular weight range 72 to 207, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or sulfonic acid groups containing olefinically unsaturated compounds such as 2-acrylamido-2-methylpropanesulfonic acid or any mixtures of such olefinically unsaturated acids.
  • olefinically unsaturated mono- or dicarboxylic acids in the molecular weight range 72 to 207, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or sulfonic acid groups containing olefinically unsaturated compounds such as 2-acrylamido-2-methylpropanesulfonic acid or any
  • the hydroxyl-containing monomers n) are used in such amounts that the abovementioned hydroxyl numbers correspond to from 0.5 to 8, preferably 1 to 5,% by weight.
  • the hydroxy-functional comonomers are used in amounts of 3 to 75, preferably 6 to 47,% by weight, based on the total weight of the monomers used.
  • the amounts of the hydroxy-functional monomers are chosen within the scope of the information provided in such a way that copolymers are formed which on average have at least two hydroxyl groups per molecule.
  • Suitable monomers n) containing hydroxyl groups are, in particular, hydroxyalkyl esters of acrylic acid or methacrylic acid with preferably 2 to 4 carbon atoms in the alkyl radical such as 2-hydroxyethyl acrylate or methacrylate, the isomeric hydroxypropyl (meth) acrylates which are formed by the addition of propylene oxide to (meth) acrylic acid, and the isomeric hydroxybutyl acrylates or methacrylates or any mixtures of such monomers.
  • the third group of olefinically unsaturated monomers o) which are generally used in the preparation of the copolymers are those olefinically unsaturated compounds which have neither acidic groups nor hydroxyl groups. These include, for example, esters of acrylic acid or methacrylic acid with 1 to 18, preferably 1 to 8, carbon atoms in the alcohol radical, such as e.g.
  • Comonomers also containing epoxy groups e.g. Small amounts of glycidyl acrylate or methacrylate or monomers such as N-methoxymethacrylamide or methacrylamide can be used.
  • the monomers of the latter third group without acid and hydroxyl groups are generally used in amounts of 5 to 90% by weight, preferably 40 to 80% by weight, based on the total weight of the monomers used.
  • the polymers A4) can be prepared by polymerization using customary processes. For example, the following are possible Bulk, solution, emulsion and suspension polymerization processes.
  • the olefinic polymers are preferably prepared in organic solution or in an aqueous emulsion. Continuous or discontinuous polymerization processes are possible. Of the batch processes, the batch and the feed process should be mentioned, the latter being preferred.
  • the solvent is initially introduced alone or with part of the monomer mixture, warmed to the polymerization temperature, the polymerization is started radically in the case of a monomer template, and the remaining monomer mixture together with an initiator mixture over the course of 1 to 10 hours, preferably 3 to 6 Hours, added. If necessary, it is subsequently reactivated in order to carry out the polymerization up to a conversion of at least 99%.
  • Aromatic solvents such as benzene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate, methoxypropyl acetate, ethers such as butyl glycol, tetrahydrofuran, dioxane, ethyl glycol ether, diethylene glycol dimethyl ether are examples of solvents.
  • Ketones such as acetone, methyl ethyl ketone, halogen-containing solvents such as methylene chloride or trichloromonofluoroethane.
  • the polymerization initiated by radicals can be triggered by initiators whose half-lives of radical decomposition at 80 to 180 ° C. are between 0.01 and 400 min.
  • the copolymerization reaction takes place in the temperature range mentioned, preferably between 100 and 160 ° C, under a pressure of 103 to 2 x 104 mbar, the exact polymerization temperature depending on the type of initiator.
  • the initiators are used in amounts of 0.05 to 6% by weight, based on the total amount of monomers.
  • Suitable initiators are e.g. aliphatic azo compounds such as azoisobutyronitrile and peroxides such as e.g. Dibenzoyl peroxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and dicyclohexyl and dibenzyl peroxydicarbonate.
  • aliphatic azo compounds such as azoisobutyronitrile
  • peroxides such as e.g. Dibenzoyl peroxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and dicycl
  • Conventional regulators can be used to regulate the molecular weight of the polymers A4), e.g. n-dodecyl mercaptan, diisopropyl xanthogen disulfide, di (methylene trimethylol propane) xanthogen disulfide and thioglycol. They are added in amounts of at most 3% by weight, based on the monomer mixture.
  • the copolymers A4) are transferred into an aqueous solution or dispersion.
  • the organic polymer solution is usually in a preheated water phase initiated.
  • the organic solvent can be removed by distillation or can remain in minor amounts in the aqueous phase.
  • a neutralizing agent such as, for example, inorganic bases, ammonia or amines
  • inorganic bases which can be used are sodium hydroxide, potassium hydroxide, and amines, in addition to ammonia, trimethylamine, triethylamine and dimethylethanolamine.
  • the neutralizing agents can be used both in the stoichiometric excess and in excess, the above-mentioned contents of sulfonate and / or carboxyl groups, in particular of carboxylate groups and the above-mentioned acid number resulting.
  • the acid number is zero, while the content of sulfonate and / or carboxylate groups corresponds to the original content of sulfonic acid groups or carboxyl groups.
  • the content of sulfonate and / or carboxylate groups corresponds to the amount of neutralizing agent used.
  • care must be taken to ensure that the polyelectrolyte character of the polymers can result in a significant increase in viscosity.
  • aqueous solutions or dispersions obtained have the above-mentioned concentrations and viscosities and generally have a residual solvent content of less than 10% by weight, preferably less than 5% by weight. on.
  • the practically complete removal of solvents boiling higher than water is possible by azeotropic distillation.
  • a likewise preferred process for the preparation of the polymer polyols A4) is the process of emulsion polymerization directly in an aqueous medium, the monomers in turn being both substances having hydroxyl groups and acid groups, i.e. Sulfonic acid or carboxyl groups, preferably monomers containing carboxyl groups, are generally copolymerized together with further monomers, after which the acid groups present are at least partially neutralized.
  • the polymers are prepared by the known process of free-radical emulsion polymerization in an aqueous medium. Continuous or discontinuous polymerization processes are again possible.
  • the batch and the feed process should be mentioned, the latter being preferred again.
  • water is introduced alone or with part of the anionic emulsifier, if appropriate with admixture of a nonionic emulsifier, and with part of the monomer mixture, heated to the polymerization temperature, the polymerization is started radically in the case of a monomer template and the remaining monomer mixture together with an initiator mixture and added to the emulsifier in the course of 1 to 10 hours, preferably 3 to 6 hours. If necessary then reactivated to carry out the polymerization up to a conversion of at least 99%.
  • the emulsifiers used here are anionic and / or nonionic in nature. Of the emulsifiers with an anionic nature, those with carboxylate groups, sulfate, sulfonate, phosphate or phosphonate groups can be used. Emulsifiers with sulfate, sulfonate, phosphate or phosphonate groups are preferred.
  • the emulsifiers can be low molecular weight or high molecular weight. The latter are e.g. described in DE-OS 38 06 066 and DE-AS 19 53 941. Those anionic emulsifiers which have been neutralized with ammonia or amines are preferred.
  • Emulsifiers which are composed of long-chain alcohols or substituted phenols and ethylene oxide chains with degrees of polymerization between 2 and 100 and a final monosulfuric acid ester group or phosphoric acid mono- and diester groups are particularly preferred.
  • Ammonia is generally used as the neutralizing agent. They can be added to the emulsion batch individually or in any mixtures.
  • Suitable nonionic emulsifiers which can mostly be used in combination with the abovementioned anionic emulsifiers, are reaction products of aliphatic, araliphatic, cycloaliphatic or aromatic carboxylic acids, alcohols, phenol derivatives or amines with epoxides such as, for example, ethylene oxide.
  • reaction products of ethylene oxide with carboxylic acids such as, for example, lauric acid, stearic acid, oleic acid, the carboxylic acids of castor oil, abietic acid, with longer chain alcohols such as oleyl alcohol, lauryl alcohol, stearyl alcohol, with phenol derivatives such as substituted benzyl, phenylphenols, nonylphenol and with longer chain amines such as dodecylamine and stearylamine.
  • the reaction products with ethylene oxide are oligo- or polyethers with degrees of polymerization between 2 and 100, preferably from 5 to 50.
  • emulsifiers are added in amounts of 0.1 to 10% by weight, based on the mixture of the monomers.
  • water-soluble and water-insoluble solvents can be considered as possible cosolvents.
  • Aromatics such as benzene, toluene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methylglycol acetate, ethylglycol acetate, methoxypropylacetate, ethers such as butylglycol, tetrahydrofuran, dioxane, ethylglycol ether, ethers of diglycol, ketones such as acetone, methylobutylchloronethoxylone, methylhexyl ketone, methyl ethyl ketone methoxyl ketone, methyl ethyl ketone, methyl ethyl ketone, cyclone are suitable, for example Am
  • the polymerization initiated by radicals can be triggered by water-soluble and water-insoluble initiators or initiator systems, the half-lives of the radical decomposition at temperatures from 10 ° C. to 100 ° C. between 0.01 and 400 min. lie.
  • the polymerization is carried out in aqueous emulsion in the temperature range mentioned, preferably between 30 and 90 ° C, under a pressure of 103 to 2 x 104 mbar, the exact polymerization temperature being dependent on the type of initiator.
  • the initiators are in quantities from 0.05 to 6% by weight, based on the total amount of monomers.
  • Suitable initiators are e.g. water-soluble and insoluble azo compounds such as azoisobutyronitrile or 4,4'-azo-bis- (4-cyanopentanoic acid) as well as inorganic and organic peroxides such as e.g. Dibenzoyl peroxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicyclohexyl and dibenzyl peroxydicarbonate as well as sodium, potassium and ammonium peroxide oxides of peroxides.
  • water-soluble and insoluble azo compounds such as azoisobutyronitrile or 4,4'-azo-bis- (4-cyanopentanoic acid
  • inorganic and organic peroxides such as e.g. Dibenzoyl peroxide,
  • peroxydisulfates and hydrogen peroxides are often used in combination with reducing agents such as e.g. the sodium salt of formamidine sulfinic acid (Rongalit C), ascorbic acid or polyalkylene polyamine. This generally leads to a significant reduction in the polymerization temperature.
  • reducing agents such as e.g. the sodium salt of formamidine sulfinic acid (Rongalit C), ascorbic acid or polyalkylene polyamine.
  • Conventional regulators can again be used to regulate the molecular weight of the polymers, e.g. n-dodecyl mercaptan, t-dodecyl mercaptan, diisopropyl xanthogen disulfide, di (methylene trimethylol propane) xanthogen disulfide and thioglycol. They are added in amounts of at most 3% by weight, based on the monomer mixture.
  • the polymers in aqueous dispersion are optionally mixed with neutralizing agents up to degrees of neutralization of 25 to 100%, preferably 35 to 100%.
  • neutralizing agents up to degrees of neutralization of 25 to 100%, preferably 35 to 100%.
  • inorganic neutralizers are used Bases, ammonia or amines added.
  • inorganic bases which can be used are sodium hydroxide, potassium hydroxide, and amines in addition to ammonia, trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, etc.
  • the neutralizing agents can be used both in the stoichiometric excess and in excess, the above-mentioned contents of sulfonate and / or carboxylate groups, in particular of carboxylate groups, and the above-mentioned acid numbers resulting.
  • the acid number is zero again, while the content of sulfonate and / or carboxylate groups corresponds to the original content of sulfonic acid groups or carboxyl groups.
  • the sulfonate and / or carboxylate group content corresponds to the amount of neutralizing agent used.
  • care must be taken to ensure that the polyelectrolyte character of the polymers can result in a significant increase in viscosity.
  • the aqueous solutions or dispersions obtained have the above-mentioned concentrations and viscosities.
  • cosolvents can remain in the aqueous dispersion in amounts of up to about 20% by weight, based on the aqueous phase.
  • the cosolvents can also be removed by distillation as required after the polymerization.
  • Component A5) is acrylate-grafted polyester resins which contain hydroxyl and carboxylate or sulfonate groups. These polymers have a molecular weight Mw of 3000 to 100,000, a hydroxyl number of 20 to 300 mg K0H / g substance and an acid number, based on all carboxyl or sulfonic acid groups, 25 to 100, preferably 100% of which are in salt form , from 5 to 75.
  • the polyesters can contain the building blocks mentioned above under a1) to a6) and optionally under a7).
  • the graft polymerization is usually carried out in 50 to 90% solution, preferably solvent-free at 90 to 180 ° C. with the use of suitable initiators, such as those of the type mentioned above and, if appropriate, with the use of suitable molecular weight regulating substances, for example those of the type mentioned above carried out, polyester and optionally solvent are introduced and monomer mixture and initiator are metered in.
  • the polymer A5) is then dispersed in water, the neutralizing agents described above optionally being added, if this has not already been done.
  • auxiliary solvents can also be used in the preparation of the polyol components A1) to A5).
  • their amount is preferably limited or, after the individual components A1) to A5) have been produced, reduced to such an extent that in the aqueous polyol component A) resulting from the mixing of the individual components and inert to the isocyanate groups of the type mentioned in an amount of at most 8% .-%, preferably at most 5% by weight and particularly preferably at most 1.5% by weight.
  • the reactive diluents mentioned as examples (which are reactive toward isocyanate groups) and which can be admixed with the individual components or, if desired, also with mixture A) of the individual components, are likewise in the aqueous solutions or dispersions A) in a maximum amount of 8% by weight, preferably at most 5 % By weight. It is particularly preferred to completely dispense with the use of such reactive diluents.
  • the aqueous solutions or dispersions A To prepare the aqueous solutions or dispersions A), the aqueous solutions or dispersions of individual components A1) to A5) mentioned by way of example mixed together in any weight ratio, it only being necessary to ensure that in the mixture at least two individual components from different groups A1) to A5) in an amount of at least 5, preferably at least 15% by weight available.
  • the preferred content of dissolved and / or dispersed polyhydroxyl compounds A1) to A5) in the aqueous solutions or dispersions A) is generally 25 to 50% by weight.
  • the polyisocyanate component B) is any organic polyisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound, free isocyanate groups which are liquid at room temperature.
  • the polyisocyanate component B) generally has a viscosity of from 50 to 10,000, preferably from 50 to 1000 mPa.s at 23 ° C.
  • the polyisocyanate component B) is particularly preferably polyisocyanates or polyisocyanate mixtures with exclusively aliphatic and / or cycloaliphatic isocyanates having an (average) NCO functionality of between 2.2 and 5.0 and a viscosity at 23 ° C. of 50 to 500 mPa.s.
  • the polyisocyanates can be used in admixture with small amounts of inert solvents in order to lower the viscosity to a value within the ranges mentioned.
  • the maximum amount of such solvents is such that in the ultimately obtained inventive Coating agents have a maximum of 20% by weight of solvent, based on the amount of water, the solvent which may still be present in the polyester dispersions or solutions also being included in the calculation.
  • Solvents suitable as additives for the polyisocyanates are, for example, aromatic hydrocarbons such as, for example, “solvent naphtha” or solvents of the type already mentioned above as examples.
  • paint polyisocyanates based on hexamethylene diisocyanate or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI) and / or bis (isocyanatocyclohexyl) methane are particularly suitable, especially those which are based exclusively on Hexamethylene diisocyanate based.
  • IPDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane
  • bis (isocyanatocyclohexyl) methane are particularly suitable, especially those which are based exclusively on Hexamethylene diisocyanate based.
  • Lacquer polyisocyanates based on these diisocyanates are to be understood as meaning the derivatives of these diisocyanates which contain biuret, urethane, uretdione and / or isocyanurate groups and which are known per se and which, following their preparation, preferably in a known manner, preferably by distillation of excess starting diisocyanate except for a residual content of less than 0.5% by weight has been exempted.
  • the preferred aliphatic polyisocyanates to be used according to the invention include polyisocyanates which have biuret groups and correspond to the abovementioned criteria Basis of hexamethylene diisocyanate, as can be obtained, for example, by the processes of US Pat. Nos.
  • the last-mentioned mixtures of viscosity at 23 ° C. of 50 to 500 mPa.s and an NCO functionality between 2.2 and 5.0 are particularly preferred.
  • aromatic polyisocyanates which are likewise suitable according to the invention but are less preferred are, in particular, "paint polyisocyanates” based on 2,4-diisocyanatotoluene or its technical mixtures with 2,6-diisocyanatotoluene or on the basis of 4,4'-diisocyanatodiphenylmethane or its Mixtures with its isomers and / or higher homologues.
  • aromatic lacquer polyisocyanates are, for example the isocyanates containing urethane groups as obtained by reacting excess amounts of 2,4-diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane and subsequent removal of the unreacted excess of diisocyanate by distillation.
  • aromatic lacquer polyisocyanates are, for example, the trimerizates of the monomeric diisocyanates mentioned by way of example, i.e. the corresponding isocyanato-isocyanurates, which have also preferably been freed from excess monomeric diisocyanates by distillation following their preparation.
  • hydrophilized polyisocyanates are particularly recommended. This facilitates the emulsification of the polyisocyanate in the aqueous phase and, in some cases, causes an additional increase in the service life.
  • Such hydrophilized polyisocyanates are e.g. by reacting di- or polyisocyanates with monofunctional polyethers of ethylene oxide and optionally propylene oxide and / or by incorporating carboxylate groups by reaction with carboxylic acids containing hydroxyl groups, e.g. 2,2-dimethylolpropionic acid or hydroxypivalic acid and their neutralization before or after the reaction.
  • the polyisocyanate component B) can also consist of any mixtures of the polyisocyanates mentioned by way of example.
  • the polyisocyanate component B) is emulsified in the aqueous dispersion A), the dissolved or dispersed component A) simultaneously taking on the function of an emulsifier for the added polyisocyanate.
  • the mixing can be done by simply stirring at room temperature.
  • the amount of the polyisocyanate component is such that an NCO / OH equivalent ratio, based on the isocyanate groups of component B) and the alcoholic hydroxyl groups of component A), is from 0.2: 1 to 5: 1, preferably 0.5: 1 to 2: 1 results.
  • the polyol component A i.e. the usual auxiliaries and additives of coating technology are incorporated into the dispersion or solution of the polyols. These include, for example, defoaming agents, leveling aids, pigments, dispersing aids for pigment distribution and the like.
  • the coating compositions according to the invention obtained in this way are suitable for practically all areas of application in which solvent-based, solvent-free or other types of aqueous coating and coating systems with an increased profile of properties are used today, for example coating of practically all mineral building material surfaces such as lime and / or cement-bound plasters , Gypsum-containing surfaces, fiber-cement building materials, concrete; Painting and sealing of wood and wood-based materials such as chipboard, fibreboard as well Paper; Painting and coating of metallic surfaces; Coating and painting of asphalt and bituminous road surfaces; Painting and sealing of various plastic surfaces; Coating of leather and textiles; in addition, they are suitable for the wide-area bonding of various materials, whereby identical and different materials are joined together.
  • mineral building material surfaces such as lime and / or cement-bound plasters , Gypsum-containing surfaces, fiber-cement building materials, concrete
  • Painting and sealing of wood and wood-based materials such as chipboard, fibreboard as well Paper
  • Painting and coating of metallic surfaces Coating and painting of asphalt and bituminous road surfaces
  • the two-component system can be cured or crosslinked after application to the respective substrate at temperatures from 0 to 300 ° C., preferably between room temperature and 200 ° C.
  • 1623 g of trimethylolpropane, 1093 g of isophthalic acid, 1185 g of Prifrac® 2950 (saturated fatty acid, from Unichema), 383 g of neopentylglycol and 608 g of hexahydrophthalic anhydride are weighed into a 6-1 reaction vessel with a stirring, cooling and heating device and water separator and under Passing nitrogen through heated to 140 ° C in one hour. The mixture is then heated to 150 ° C. in 3 hours and to 220 ° C. in 7 hours. It is condensed with elimination of water until the polyester has a total acid number of 2.8 and an OH number of 216.
  • the polyester thus obtained containing urethane, carboxyl and hydroxyl groups is dispersed in an NH 3 / water mixture such that an aqueous dispersion of the polyester polyol component Al) with a solids content of approx. 48.5%, a pH of approx. 7.4 , a degree of neutralization of 100%, an acid number of about 10 and a hydroxyl group content of about 4.6 is obtained.
  • 106.8 g of tetrahydrophthalic anhydride are added all at once and kept at 120 to 130 ° C. until the total acid number is approx. 45 is.
  • 200 g of dimethyl diglycol and 50 g of NMP are added and the resin melt is dispersed in a water / triethylamine mixture at approx. 80 ° C.
  • the aqueous polyester dispersion A2) then has a solids content of approx. 38%, the degree of neutralization is approx. 90%.
  • the hydroxyl group content is approx. 3.5%.
  • 280 g of neopentyl glycol, 180 g of trimethylolpropane, 317 g of 1,6-hexanediol, 265 g of phthalic anhydride, 82.5 g of 5- (lithium sulfo) isophthalic acid and 0 are placed in a 5-1 reaction vessel with a stirring, cooling and heating device and water separator , 75 g of dibutyltin oxide weighed and heated to 175 ° C in 1 hour under N2 atmosphere. The mixture is esterified at 175 ° C. until the solution has become clear, then 478 g of phthalic anhydride are added and the mixture is heated to 200 ° C. It is heated until an acid number ⁇ 10 is reached.
  • aqueous dispersion of a polyester resin A3) containing sulfonate and hydroxyl groups is obtained, which has a solids content of about 35% and a hydroxyl group content of about 4.8%.
  • 166.7 g of the polyester precursor and 36.7 g of butylglycol are weighed into a 2 l reaction vessel with a stirring, cooling and heating device and heated to 125.degree.
  • a mixture of 83.3 g of n-butyl acrylate, 100.0 g of hydroxyethyl methacrylate, 141.7 g of methyl methacrylate and 3.3 g of n-dodecyl mercaptan is metered into the polyester solution within 2 hours.
  • a mixture of 41.7 g of n-butyl acrylate, 50.0 g of hydroxyethyl methacrylate, 70.8 g of methyl methacrylate, 12.5 g of methacrylic acid and 1.7 g of n-dodecyl mercaptan is then added within 1 hour.
  • Starting with the addition of monomers 17.9 g of tert-butyl per-2-ethylhexanoate (70% in a hydrocarbon mixture) are metered in in parallel over the course of 4 hours. After the end of the peroxide addition, stirring is continued at 125 ° C. for 2 hours,
  • the grafted polyester resin is neutralized with 19.6 g of dimethylethanolamine and dispersed with 780 g of water. A fixed content of approx. 43.2% is set by adding water.
  • the polyester resin A5) grafted with vinyl monomers has an OH content of about 5.2% and an acid number of about 18 mg KOH / g solid resin.
  • the degree of neutralization is approximately 100%.
  • aqueous polyacrylate dispersion A4 50 parts by weight of the aqueous polyacrylate dispersion A4) are mixed with 50 parts by weight of the aqueous dispersion of the urethanized polyester A1).
  • the lacquer applied in a wet film thickness of 200 ⁇ m initially appears milky cloudy, but becomes completely clear and transparent within 30 to 60 minutes at room temperature, i.e. with increasing evaporation of the water.
  • the applied paint film has a dust drying time of approx. 2 to 3 hours. The final curing takes 10 to 14 days.
  • the hardened paint film then has the following range of properties: Optics (gloss / transparency): very good Pendulum hardness (Albert / König): 100-120 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: very good Acetone: good-moderate Ethanol: Well
  • the same property profile is also achieved by forced drying at elevated temperatures, for example 1 h at 80 to 100 ° C or baking, for example 30 minutes at 130 to 150 ° C.
  • polyester dispersion A1 25 parts by weight of polyester dispersion A1) are mixed with 75 parts by weight of polyacrylate dispersion A4) to form a polyol component A).
  • polyacrylate dispersion A4 25 parts by weight of polyacrylate dispersion A4.
  • polyisocyanate 1 24.44 parts by weight of polyisocyanate 1 are now added to the preparation described above and homogenized by simple stirring. This creates a two-component polyurethane lacquer in an aqueous phase with a processing time of approx. 5 hours.
  • the NCO / OH ratio is 1.5.
  • aqueous two-component polyurethane lacquer applied in a wet film thickness of 200 ⁇ m initially appears milky cloudy, but it becomes completely clear and transparent within 30 to 60 minutes at room temperature, i.e. with increasing evaporation of the water. Dust drying takes 2 to 3 hours. The final curing takes 10 to 14 days.
  • the paint film then has the following range of properties: Optics (gloss / transparency): very good Pendulum hardness: 90-110 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: very good Acetone: good-moderate Ethanol: Well The statements in Example 1 apply with regard to behavior with forced drying or stoving hardness.
  • the cured paint film has the following range of properties: Optics (gloss / transparency): very good Pendulum hardness (Albert / König): 80-100 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: very good Acetone: good-moderate Ethanol: Well The statements made in Example 1 regarding forced drying at elevated temperatures or baking curing also apply here in full.
  • Example 4 corresponds to Example 3, with the difference that the same amount of a polyester dispersion A2) is used instead of the polyacrylate dispersion A4).
  • the cured paint film has the following range of properties: Optics (gloss / transparency): very good Pendulum hardness: approx. 80 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: very good Acetone: good-moderate Ethanol: good-moderate
  • Example 5 corresponds to Example 2, with the difference that instead of polyester dispersion A1), the same amount of polyester dispersion A3) is used.
  • the cured paint film has the following range of properties: Optics (gloss / transparency): Good Excellent Pendulum hardness: approx. 100 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: very good good Acetone: good-moderate Ethanol: Well
  • Example 6 corresponds to Example 3, with the difference that instead of the polyester dispersion A1) the same amount of the graft polyester dispersion A5) is used.
  • the cured paint film has the following range of properties: Optics (gloss / transparency): Good Excellent Pendulum hardness: 120-130 sec Resistance to solvents White spirit: very good Solvent Naphtha 100: very good Methoxypropylacetate: Good Excellent Acetone: Well Ethanol: Well

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Claims (10)

  1. Liant combiné aqueux consistant essentiellement en
    A) une solution ou dispersion aqueuse d'un composant polyol organique diluable à l'eau et
    B) un composant polyisocyanate ayant une viscosité à 23°C de 50 à 10 000 mPa.s, qui consiste en au moins un polyisocyanate organique à l'état émulsionné dans le composant A), avec un rapport de 0,2:1 à 5:1 entre les équivalents de groupes isocyanates du composant B) et les équivalents de groupes hydroxy du composant polyol de A),
    caractérisé en ce que le composant polyol diluable à l'eau de A) est un mélange d'au moins deux polymères portant des groupes hydroxy, choisis dans les groupes A1), A2), A3), A4) et A5) ci-après :
    A1) les résines de polyester portant des groupes hydroxy, uréthanes et carboxylates, et à un poids moléculaire Mw = 3 000 à 100 000, un indice d'hydroxyle de 20 à 240, un indice d'acide rapporté à tous les groupes carboxyles qui sont pour 25 à 100 % à l'état de sel, de 8 à 60, et une teneur en groupes uréthanes
    Figure imgb0004
     de 1,0 à 15,0 % en poids,
    A2) des résines de polyester contenant des groupes hydroxy et carboxylates mais exemptes de groupes uréthanes et de groupes sulfonates, à un poids moléculaire Mw de 1 000 à 50 000, un indice d'hydroxyle de 15 à 240 et un indice d'acide, rapporté à tous les groupes carboxyles qui sont pour 25 à 100 % à l'état de sel, de 15 à 90,
    A3) des résines de polyester contenant des groupes hydroxy et sulfonates et, le cas échéant, des groupes carboxylates et/ou des groupes uréthanes, à un poids moléculaire Mw de 1 000 à 50 000, un indice d'hydroxyle de 15 à 240 et un indice d'acide, rapporté à tous les groupes acides sulfoniques et, le cas échéant, carboxyles, qui sont pour 25 à 100 % à l'état de sel, de 3 à 45,
    A4) des résines de polyacrylates contenant des groupes hydroxy, carboxylates et/ou sulfonates, à un poids moléculaire Mw de 500 à 100 000, un indice d'hydroxyle de 15 à 270 et un indice d'acide, rapporté à tous les groupes carboxyles et acides sulfoniques qui sont pour 25 à 100 % à l'état de sel, de 5 à 125 et
    A5) des résines de polyesters greffés par des acrylates, contenant des groupes hydroxy, carboxylates et/ou sulfonates, à un poids moléculaire Mw = 3 000 à 100 000, un indice d'hydroxyle de 20 à 300 mg de KOH/g de substance et un indice d'acide, rapporté à tous les groupes carboxyles et acides sulfoniques, qui sont pour 25 à 100 % à l'état de sel, de 5 à 75,
    sous réserve que, dans le composant polyol, il y ait au moins deux représentants de groupes différents parmi les groupes A1) à A5), présents chacun en proportion d'au moins 5 % en poids.
  2. Liant combiné aqueux selon revendication 1, caractérisé en ce que dans A), il y a au moins un composant polyol A1) qui a été préparé par réaction de
    a) 65 à 94 % en poids d'un polyesterpolyol d'indice d'hydroxyle 50 à 500 et d'indice d'acide ≤12,
    b) 0 à 35 % en poids d'au moins un composé mono- à tétra-fonctionnel au sens de la réaction d'addition des isocyanates, à un poids moléculaire de 32 à 2 000, différant des composés a) et c) et contenant des groupes amino et/ou hydroxy,
    c) 2,0 à 7,5 % en poids d'un acide 2,2-bis-(hydroxyméthyl)alcanecarboxylique ou de la quantité correspondante, par les proportions, d'un sel de tert-amine d'un tel acide et
    d) 5 à 30% en poids d'au moins un composant isocyanate, au moins difonctionnel de poids moléculaire 168 à 1 500,
    ou par réaction de
    e) 60 à 97 % en poids d'un polyesterpolyol d'indice d'acide 50 à 500, de préférence 80 à 350 mg de KOH/g de substance et d'indice d'acide ≤12,
    f) 2 à 20% en poids d'un anhydride d'acide di- et/ou tri- et/ou tétracarboxylique et
    g) 0,1 à 20% en poids d'au moins un composant isocyanate, au moins difonctionnel, de poids moléculaire 168 à 1 500,
    suivie dans chaque cas de la neutralisation au moins partielle des groupes carboxyles.
  3. Liant combiné selon revendications 1 et 2, caractérisé en ce que dans A), il y a un composant polyol A2) qui a été préparé par réaction de
    h) 75 à 98 % en poids d'un polyesterpolyol d'indice d'hydroxyle de 50 à 500 mg de KOH/g de substance et à un indice d'acide inférieur ou égal à 12 mg de KOH/g de substance et
    i) 25 à 2% en poids d'un anhydride d'acide di- et/ou tri- et/ou tétracarboxylique,
    suivie de la neutralisation d'une partie au moins des groupes carboxyles.
  4. Liant combiné selon les revendications 1 à 3, caractérisé en ce que dans A), il y a un composant polyol A3), qui a été préparé par réaction de
    a1) 0 à 60 % en poids d'acides monocarboxyliques de poids moléculaire 112 à 340,
    a2) 10 à 65 % en poids d'acides polycarboxyliques de poids moléculaire 98 à 600 ou de leurs anhydrides,
    a3) 5 à 70 % en poids d'alcools difonctionnels et à plus forte fonctionnalité de poids moléculaire 62 à 2 000,
    a4) 0 à 30 % en poids d'alcools monovalents de poids moléculaire 100 à 299,
    a5) 0 à 15 % en poids d'acides hydroxycarboxyliques de poids moléculaire 90 à 280 ou leurs lactones,
    a6) 0 à 15 % en poids d'aminoalcools de poids moléculaire 61 à 300 et/ou d'acides aminocarboxyliques de poids moléculaire 75 à 260, et
    a7) 0,5 à 25 % en poids d'un composant de synthèse portant des groupes sulfonates et choisi parmi les alcools portant des groupes sulfonates et les acides carboxyliques aromatiques portant des groupes sulfonates.
  5. Liant combiné selon les revendications 1 à 4, caractérisé en ce que dans A), il y a au moins un composant polyol A4), qui a été préparé par copolymérisation de
    m) 0,3 à 30 % en poids de monomères portant des groupes carboxyles et/ou acide sulfoniques
    n) 3 à 75 % en poids de monomères à fonctions hydroxy et
    o) 5 à 90 % en poids d'autres monomères copolymérisables,
    suivie de la neutralisation au moins partielle des groupes salifiables.
  6. Liant combiné selon les revendications 1 à 5, caractérisé en ce que dans A), il y a au moins un composant polyol A5), lequel est un produit de greffage qui a été obtenu en soumettant à une copolymérisation greffée
    p) 95 à 10 % en poids d'un mélange de monomères contenant
    m) des acides carboxyliques α,β-insaturés
    n) des monomères α,β-insaturés à fonctions hydroxy,
    o) d'autres monomères copolymérisables
    en présence de
    q) 5 à 90 % en poids d'un polyesterpolyol d'indice d'hydroxyle 10 à 500, indice d'acide maximum 30, teneur en doubles liaisons oléfiniques (exprimée en C=C, poids équivalent = 24) de 0 à 10 % en poids,
    les pourcentages indiqués se complétant à 100 % en poids.
  7. Liant combiné selon les revendications 1 à 6, caractérisé en ce que le composant polyisocyanate B) consiste en un ou plusieurs polyisocyanates organiques à groupes isocyanates à liaisons exclusivement (cyclo)aliphatiques.
  8. Liant combiné selon les revendications 1 à 7, caractérisé en ce que le composant polyisocyanate B) est mis en oeuvre à l'état hydrophilisé par des polyéthers monofonctionnels et/ou des groupes carboxylates.
  9. Procédé de préparation de liants combinés selon les revendications 1 à 8, caractérisé en ce que, dans une solution ou dispersion aqueuse d'un composant polyol A) qui consiste en un mélange d'au moins deux composants individuels choisis dans les groupes A1), A2), A3), A4) et A5) définis dans la revendication 1, on émulsionne un composant polyisocyanate ayant une viscosité à 23°C de 50 à 10 000 mPa.s et qui consiste en au moins un polyisocyanate organique, avec des proportions relatives des deux composants correspondant à un rapport de 0,2:1 à 5:1 entre les équivalents de groupes isocyanates du composant polyisocyanate et les équivalents de groupes hydroxy du composant polyol, les produits auxiliaires et additifs et, le cas échéant, les diluants réactifs, éventuellement utilisés conjointement, étant incorporés à la solution et/ou dispersion du polyol avant l'addition du composant polyisocyanate.
  10. Utilisation des liants combinés selon les revendications 1 à 8 en tant que liants pour des vernis, des produits de revêtement et des masses d'étanchéité, ainsi que pour des colles.
EP92118831A 1991-11-14 1992-11-03 Combinaison aqueuse de liants, procédé de sa préparation et son utilisation Expired - Lifetime EP0542105B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4137429 1991-11-14
DE4137429A DE4137429A1 (de) 1991-11-14 1991-11-14 Waessrige bindemittelkombination, ein verfahren zu ihrer herstellung und ihre verwendung

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EP0542105A1 EP0542105A1 (fr) 1993-05-19
EP0542105B1 true EP0542105B1 (fr) 1996-01-24
EP0542105B2 EP0542105B2 (fr) 2007-04-11

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EP (1) EP0542105B2 (fr)
JP (1) JP2923718B2 (fr)
KR (1) KR100217448B1 (fr)
AT (1) ATE133430T1 (fr)
CA (1) CA2082785A1 (fr)
DE (2) DE4137429A1 (fr)
ES (1) ES2084909T5 (fr)
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CN106497459A (zh) * 2001-07-20 2017-03-15 罗姆和哈斯公司 含水混合粘合组合物和制法

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DE59205158D1 (de) 1996-03-07
US5331039A (en) 1994-07-19
KR930010143A (ko) 1993-06-22
EP0542105B2 (fr) 2007-04-11
CA2082785A1 (fr) 1993-06-15
JPH05295072A (ja) 1993-11-09
MX9206387A (es) 1994-06-30
JP2923718B2 (ja) 1999-07-26
EP0542105A1 (fr) 1993-05-19
KR100217448B1 (ko) 1999-09-01
ES2084909T5 (es) 2007-11-16
ATE133430T1 (de) 1996-02-15
DE4137429A1 (de) 1993-05-19
ES2084909T3 (es) 1996-05-16

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